Selective hydrogenation of butadiene in admixture with butenes with cobalt molybdateas catalyst



Apnl 26, 1960 c. K. VILAND 2,934,574

SELECTIVE HYDROGENATION OF BU'IADIENE IN ADMIXTURE WITH BUTENES WITH COBALT MOLYBDATE AS CATALYST Filed Jan. 11, 1957 2 Sheets-Sheet 1 8 FLUIDIZED GOKING .9 /0 l +coKE CRACKED EFFLUENT FRAOTIONATION :xmme: c, AND HEAVIE my. To 20% H2 /2 4% T0 10% qs CONTAINING AND LIGHTER 50%1'0 10% BUTYLENES L 2% T0 8% BUTADIENE I4 SELWTWE can; r uoL man 7: CA TAL rsr HY DROGENATION "a, CONTENT: 19'. sueumr azouceo eurneues: DE-BUTADlENE-IZED was 4 suasmumuv SAMEOR BUTADIENE: MORE FRAOTIONATION 0, AND LIOHTER qsmem ALKYLATION POLYMERIZATION INVENTOR.

CLARE KENNETH V/LAND AGENT April 26, 1960 c. K. VILAND 2, 3

ssuzcnvz HYDROGENATION OF BUTADIENE m ADMIXTUREI WITH BUTENES WITH COBALT MOLYBDATE AS CATALYST Filed Jan. 11, 1957 2 Sheets-Sheet 2 mx'runc OF CRACKED GASES BUTYLENES mo mcLuomo aummzm: H2 7 cgs AND H:

201 l 30 l 2/ SELEGTIV E 3 HYDROGENATION FRAN'ONAT'ON 'u k a 5 2 i 22 1 3 i; BUTYLENES WITH c,To 0 o ONLY A TRACE OF E BUTADIENE I" 2 .l a 5 c mx1'una 2% TO 61. BUTADIENE EXCESS can r ssuzcnvs uomuur: 3 uvonoeenmou SUBSTANTIALLY BUTAOIENE -FREE mxrunz OF Q'S ALKYLATION INVENTOR.

CLARE KENNETH V/LAND AGE/VT SELECTIVE HYDROGENATION OF BUTADIENE IN ADMIXTURE WITH BUTENES WITH COBALT MOLYBDATE AS CATALYST Clare Kenneth Viland, Martinez, Califl, assignor to Tidewater Oil Company, a corporation of Delaware Application January 11, 1957, Serial No. 633,800 Claims. (Cl. 250-677) This invention relates to treatment of hydrocarbons containing four carbon atoms and more particularly to the conversion of butadiene into'butylene, without subv.

stantially affecting butylenes already contained in the mixture. The invention also relates to-the treatment of the elfluentgas from a fluidized coking operation to prepare its 0.; content for alkylationand/or polymerization. 1 When heavy petroleum stocks are treated by such processes as fluidized coking to convert them to'more desirable lower boiling products, a substantial amount, i.e., usually between 2% and 3% of the effluent, coinprises mixtures of various C hydrocarbons. In the C mixture, there are substantial amounts of butane, isobutane, and butylenes such as buten'e-l and butene-2. However, diolefins such as butadiene'are also present, in amounts between 2% and 6% of the C, content, depending partly upon the-original stock and partly'on thetr eat-' ment thereof. i

' Now, a mixture of isobutane and butylene is very dustry War Council stated in. their Report No.'AMO 1,

A Digest of Dataon Alkylation, dated February 1, 1943 (p.9):

. impurities in the feed may cause greatly increased acid consumption. The'most undesirable impurities are V g 2,934,574 P r AP. 1 9

a mixture free from butadiene and containing increased quantities of butylene. f

Another object of the invention is toenable the use of the C fractions from fiuidizedcoking operations in 'alkylation' and polymerization processes by converting substantially all the butadiene therein to more useful C;

compounds, thereby both eliminating the trouble-causing butadiene and increasing the amount of C compounds usable in alkylation or polymerization.

Another object of the invention is to provide a method of de-butadiene-iz ing the C and lighter fractions of the efliuent from fluidized coking operations before separat 'ing t-hecornponents of this light fraction of the efiluent by further fractionation, so that the hydrogen present in n the effluent can be used with suitable catalysts to effect a conversion ofbutadiene to butylenes. Asa result, a step is saved, as compared with first fractionatin'g and then re-adding some of the fractionated hydrogen.

Other objects and advantages of the invention :Will appear from the following description. w

The invention comprises passing the mixture of butadime and butylene over a cobalt molybdate hydrogenation catalyst in conjunction with at least the mole amount of hydrogen. I have found that this oanbe done without essentially lowering the amount of valuable C s present and that selective hydrogenation takes place so that, while the diolefins are converted to olefins, very little if any of the olefins already present are converted to saturated butane. An understanding of the method will be better gained bystudying the flow-sheets accompanying this specification.

In the drawings: Fig. l is a flow-sheet of a method embodying the principles of the present invention, as applied to fluid, coking.

5 Fig.2 is a condensed flow-sheet of the basic method of the invention. V n Fig. 3 is 'a flow-sheet of a'modified formof the method embodying the principles of this invention. V

' Fig'. 1 shows a' typical example of the application the invention to afluidized coking operation, wherein probably (ii-olefins, which appear to have the. property of l causing far more than stoichiometric degradation of the acid, as if they initiated some chain of-reactionsQthe' mechanism of which has not yet beenrdelineated, It has been observed, however, byStandard Oil Company of Louisiana, that butadiene in a mixed ,butylene feed causes spending ofi'the acid correspondingto30 pounds of acid per gallon of butadiene contained in the feed Butadiene also results in the formation of various compounds and polymers inimical to stabilization'of the resultant ismoctane. In other word's butadiene polymers "ins 15. .5 'flui z dpok n operatio he bu wli'ereev r there i a ixt reo o-olefin i nq l iol finia C4 hy drocarbons, either as a separated fraction orin'Jcombinationwith other gases.

One important object a lready present.

' nml b ect on of the present invention is, to ,provide a method for hydrogenatin'g' the diolefins present inaC mixture to"olefins,without gtfecting the' olefins 70 he invention; is to convertjthe; butai-i in each molecule'of butadiene, replacing it with two atoms 'ene'pre'sent in a mixture 'ofbutadiene butylenes to r heavy residual hydrocarbon oils 7 from various parts of the refinery-are treated by fluidized coking 8. Coke 9 is drawn off as a by-product,,while the, desired cracked effluent 1 0 is'alsorecovered and fractionated at 11 to separate the heavy portions 12mm the normally gaseous frac'tion13. Any standard fluidized coking reaction may be used; soit is unnecessary to show the coking process in detail, many issued patents'in this field being available for reference. A typical example of the cracked effluent 10 contains about 88% to 84% by weight of C s and heavier, and approximately 12% to,l6% by weight of the normally gaseous fraction 13. The fraction 13 may have a molal' content somewhere between 10% and 20% of hydrogen '(normally around, 13% to 16%),-6Q% of C and C gases, 10%-44% of C gases, and, depending largely" upon the constitution of theresidual oil 7, between 4% and 10% of C gases. Analysis of the C gases in'typical runs has shown that butadiene is normally present at about 2 to 8 mole. percent of the C; content; the remaining C gases being. butane, iso-butane, butene-l and butene-Z. It is the butadiene that gives the trouble.

In the specific example of the invention shown in 'Fig. l, the entire light fraction 13,,without further fractionation, is selectively hydrogenated at 14 at the'proper temperature and space velocity over cobalt molybdate as a catalystin the presence of. heat and pressure. a Sorne of the hydrogen present breaks one of the double -bonds t 'yldrq a a in Wha r sz aa s h wad sna to butylene, some of it being butene-l, and some butene-Z, but predominately butene-2. As the next step, the hydro genated fraction may be fractionated at 16 to provide 'a predominately C fraction 17. Then the butadienefree C fraction 17 may be either alkylated at 18 or polymerized at 19, depending upon'what is desired, with the resultant formation of iso-octane or other desirable fuel constituents which may be blended directly into the gasoline.

The abbreviated diagram, Fig. 2, shows the basic method: A mixture 20 of mono-olefinic and diolefinic C with or without other hydrocarbons being present, is catalytically hydrogenated at 21 over cobalt molybdate, the hydrogen 22 being either already mixed with the C mixture or added separately. The result 23 of the reaction is the elimination of the butadiene and the formation of more butylene.

An alternative form of the invention is shown in Fig. 3. Here, a cracked effluent 30 containing between 4 and 10 mole percent of the C gases, fractionated at 31 where it is first separated into anH fraction 32, a fraction 33 of C s, and other fractions 34. The 0, mixture 33, containing between 2 and 8 mole percent of .butadiene, is catalytically hydrogenated at 35 over cobalt .molybdate along with some of the hydrogen 32. The hydrogen may be present in any amount from equal mole volumes up, since the two atoms of hydrogen in each molecule are sufiicient to hydrogenate one molecule of the diolefin, adding one hydrogen atom to each of the two carbon atoms formerly joined by the second double-bond. After hydrogenation, the butadiene has been eliminated, and the mixture 36 consisting only of butane, iso-butane, .and butylenes may be fed directly to alkylation at 37 for conversion to iso-octane and other valuable heavier hydrocarbons.

Which precise form the'process takes depends upon the requirements of the particular refinery, upon the constituents of the residual oil fed to the coking operation,

:and upon the type of equipment available or chosen. Preferably, the hydrogenation step is done after com pression. Where the hydrogenation step precedes separation into fractions, pentadiene, propadie'ne and other fractions similar to butadiene may also be converted to mono-olefins at the same time. In a typical example, the temperature may lie in the range of 300 F. to 600 F. and preferably lies in the range of 400 F. to 450 F.;

the space rate may lie between 200 and 10,000, prefer- V ably between 1000 to 3000, standard cubic feet of gas A per cubic foot of cobalt molybdate. (These space velocities correspond roughly to liquid hourly space velocities of 1 to 40 cubic feet of liquid per cubic feet of catalyst for the broad range and 4 to 12 for the preferred range.) With higher space-rates, higher temperatures are desirable to produce sufliciently severe conditions, while with lower space rates, lower temperatures may be used. .The pressure conditions are less critical and may vary rather widely, as from about 30 p.s.i.g. to about 300 improved results in the alkylation or polymerization plant.

Several examples follow.

EXAMPLE I A simulated fluid coking fraction was obtained by adding butadiene to a sample of the C fraction from a cat.- alytic cracker in approximately the proportions normally found in fluidized coking. The simulated fraction t then hydrogenated over cobalt molybdate. A study of the operating variables is summarized in Table 1.

Table 1 HYDROGENATION OF SIMULATED FLUID (JOKER 0. FRACTION Run No 1 2 3 4 5 7 Operating Conditions:

Temperature (Max), F 575 300 598 530 558 Pressure, p.s.i.g 200 200 200 200 Liquid hourly space velocity (LHSV) 20 20 10 40 H: recycle rate, s.c.t./Bb1.. 100 100 200 200 100 Moles Hz/IIIOIB butadiene. 2. 1/1 2. 111 4. 2/1 4. 2/1 2. 1/1

Product Feed Analysis (Mole Percent):

Butadiene 3. 8 0.0 3. 3 0. 1 0.0 1. 2 Butylene 55. 7 55.3 56. 1 53.1 52. 2 57. 4

A comparison of runs 1 and 5 shows that LHSVs much above 20 results in incomplete saturation of butadiene, while a comparison of runs 1 and, 3 appears to show that increased amounts of hydrogen resulted in a loss in butylene content as though due to conversion of some of the butylene to butane and iso-butane. However, see. the results of Table 5.

EXAMPLE II Table 2 HYDROGENATION OF TOTAL FLUID COKER 048 AND LIGHTER Run Nam; s 1 s 9.

Operating Conditions: Temperature, F 300 500 600 500 Pressure, p.s.i.g 55 55 150 Space velocity (s. 200 1,000 5, 000 3, 000

Product Feed 0.2 trace trace trace trace Olefins (C3, 0;, C 16.5 13. 13.5 14.0 12.9

Runs 6, 7, and 8 show that approximately the same results are obtained with space velocities of 200 at 300 F. and 55 p.s.i.g., 1000 at 500 F. and 55 p.s.i.g., and 5000 at 500 F. and 150 p.s.i.g. Lower space velocities of course increase the amount of hydrogenation (runs 8 and9).

The fact that an excess of hydrogenrwas present was indicated also by the saturation of some of the ethylene, propane and butylene present.

EXAMPLE 1H The gas from a fluid coking plant with hydrogen and the gases C; and lighter was run directly into a hydrogenation catalytic apparatus. .The results are shown in the data on Table 3.

Table 3 Operating conditions: a Run No. 10 Reactor temperature F..- 400 Reactor pressure ..p.s.i.g S5 V./hr./v. (gas volumeper hour per volumeof catalyst in reactor) 1660 001112211100: 01? has boMEosrrIoN BEEoEE AND AFTER REACTION Before fatter Propylene 6.3 5. 2

' Propane..- 5.9 6.7 .0; Gases 7.4 7.4

OIIEiactlon-Mole Percent of Total Q s: I a Butad1ene; i;' 2.5 0.0

Butane-1 7 28.8 "2612 Butane-2-.---- 14.4 20.1 Iso-Butylene 22. 6 22 2 Total Buty1enes. .L 65. 8 68.5 Iso Bu ne a 1 6.5 5. 2

Bntane; 25.2 26.3 100.0 100.0

EXAM IV.

I Table 5" OPERATING CONDITIONS 1N EXAMPLE v Run N0 13 14 15 16 17 Reactor Pressure, p.s.i.g v200 200 200' 200 200 Maximum Catalyst Temp., F 389 333 359' 474 a 404 LHSV Feed 7. 5 5. 2v 5. 2 7. 5 5. 2 V./Hr./V. Feed 1 7 1,900 1,300 V./Hr./V. Feed+hydr0gen 2, 200 2, 300 3, 100 2, 200 2, 300 Hydrogen to Butadiene Ratio"-.. 3. 0 10. 2 18. 3 3. 0 10. 2 Butadiene Percent Removal 30 72 76 89 Gain in Butylenes, Mole Percent 1. 3 2. 6 3. 9 3. 2 3. 6 Gain in Butylenes, Percent Theoretical 99. 6 99. 4 99. 6 98. 7 98. 3

1 B.e.t. per hour of gas per e.f. catalyst.

The specific composition (mole percentlof the charge and of the treated mixture is shown in Table 6. w

Table 6 COMPARISON OF GAS OOMPOSITION IN MOLE PERCENT BEFORE AND. AFTER REACTION IN EXAMPLE V Run No Charge 13 14 15 16 17 NH-CO- Hydrogen' 8.9 45.9 57;0 44:0 Methane. 0.1 Ethylene 1.6 0 8 0:7 0.8 Ethane 0.1 0.1 Propyle 0.4 0.2 0.1 t. Propane 1.8 1.6 0.9" 0.7' 1:5 1.0. 5.3 3.3' 1.2 0.6 1.1 0.3 V 27.0 24.9 14.5 9.1 28.5 8.7 6.9 7.3 5.1 7.0 6.0 12.3 Iso-Butylene 30. 0 26. 0 '16. 0 12. 7 25. 5, 16. 1 (Total Butylenes).- (63. 9) (58. 2) (35.6) (28. 8) (60.0) (37. 1) Iso-Butane 5. 6 5. 2 3. 3. 2. 7" 5. 1 3. 3 n-Butane.-- 22.6 20.2 11.9 9.3 20.8 12.8 Amylenes" 0.1, 0.3 0.1 0.1 0.2 0.2 Isq-Pentane 0. 3 0. 4 0. 2 0. 1 0. 4 0. 3 Total 100. 0 100. 0 100. 0 100. 0 100. 0 100.0.

Table 4 7 C GAS COMPOSITION BEFORE AND AFTER REACTIONS,

MOLE'PERCENT OF TOTAL CBS Eunno.. 11 12 7 Reactor Temperature, F 310 475 Reactor Pressure,p.s.1.g 55 YeIH -I -Q- 1,220

Before After 0.1.... arter IButadiene. 3.4 1.8 4.9 0.0 Total Butylenes. 67. 8 66. 6 65. 8 61. 5 Iso-Butane. 1.7 5.3 4.9 7.7 n-Butane 27.1 26. 3 24. 4 30. 8

EXAMPLE V It will be recalled that a comparison of runs 1 and 3 indicated that an excess of hydrogen might saturate some of the butylenes. Further tests were therefore run with high hydrogen-to-butadiene ratiosup to about 20 to 1. But no significant loss in butylene content was observed under the conditions of these further tests, as shown in Table 5. Differences in temperatures, pressures and space velocities did, however, produce further difierences. In

this example, the hydrogenused was pure cylinder hydros a blend of C hydrocarbons gen, and the charge stock was those obtained from fluid of the same composition as coker operations (cf. Fig. 3).

An analysis of the C fraction Table 7 o. FRACTION or EXAMPLE MOLE PERCENT OF our. i

nN Charge 14 15 r 10 17 Butadiene 5.4 as 24 1.5 1.3' 0.0 Butene-1 27. 7 2s. 7 27. s 21. s 32. 1 10. 2 Bntene-2- 7. 1 8. 4 9. 7 17. O 6. 9 23. (I Iso-Butylen 3o. 0 29. 9 30. s so. 5 29. a 30.1 (Total Buty 05. 1 07. 0 0s. a 09. a as. 9 09. a Iso-Butane 5. 7 6.0 "6.4 Y 6.6 5.9 6.2 n-Butarle 23. 2 23. 2 22. 9 22. v0 23.9 g

Total. 100.0 100.0 100.0 100.0 100.0 100.0

EXAMPLE VI Additional tests were run with the same charge stock as in Example V, but with the hydrogen being obtained from the discharge of a catalytic reformer compressor. Theactual composition of this hydrogen. charge 57 I The operating conditions-of this Example are shown in Table9... M,

V 7, Table 9 V V OPERATING CONDITIONS IN EXAMPLE VI 7 Run No 18 19 20 Reactor Pressure, p.s.i.g-.-;. 201 r 201 r i 201 Maximum Catalyst Temp., F '410 430' 425 LHSV Feed 7. 5 10. 9' 7. 5 V./Hr./V. Feed 1 1, 900 2, 600 1, 900 VJHLIV. Feed+Hydrogen. 2, 100 3, 000 2, 200 Hydrogen to Butadiene Ratio. 1.7 3. 5 2. 7 Butadlene Percent; Removal... 22 30 33 Gain in Butylenes, Mole Percent "'0. 4' 1. 3 1. 3 Gain in Butylenes, Percent Theoretical 98. 8 99. 6 99. 3

Sci. per hour of gas per c.f. catalyst. V The g ascompositions concerned are shown in.Tab1e 10. Table I OOIPARISON 0F GAS COMPOSITION (MOLE PERCENT) EFORE AND AFTER REACTION IN EXAMPLE VI Run No-.-.' Charge 18. 19 20 "'ifi' ""it' "if' 0. 1 0. 6 0. 2 1.6 1.4 1.5 4 0.1 0.3 0.2 Is 'ifs' ""if ""ifiz" 3 3. 5 3. 2 3. 1 .0 25.8 23.7 26.4 .9 1.2 6. 5 6.8 0 27. 7 26. 9 25. 8 .9) (54. 7) (57. 1) (59.0) .6 4.9 4.8 5.4 6 19.5 20. 1 20. 3 .1 0.3 0.3 0.2 .3 0.3 0.4 0.5

Total 100. 0 100. 0 100. 0 100. 0

Table 11 shows the detailed analysis of the C fraction.

Table 11 o, FRACTION IN EXAMPLE MOLE PERCENT OF TOTAL Run No Charge is 19 20' Butadiene. 5. 4 4. 2 3. 8 3. 6 Butane-1 27. 7 a1; a '27. a so. 0 Butene-2...-.' 7. 1 1. 4 7.6 7. 7' Iso-Butylene 30.9 33.4 31. 5 29.3 (Total Butyle (65.7) (66.1) (67.0) (67.0) Isa-Butane... 5. 7 6. 0 5. 6 6. 2 n-Butane---- 23. 2 23. 7 23. 6 23. 2

Total 100.0 100.0 100.0 100. 0

Having described the invention and illustrated its application by specific examples, I claim:

1. A process for eliminating butadiene from a dry mixture thereof with butylenes, comprising hydrogenatingthe dry mixture in the presence of cobalt molybdate catalyst at between 300 F. and 600 F. and at a vapor space velocityrbetween 200 and 10,000 volumes of gas gser'volumeot catalyst, to convert the butadiene to butylene'while leaving the original butylene substantially unchanged. "2: The process of claim 1, wherein the hydrogenation iscarried on at between 400 F. and 450 F. and at a vapor space velocity of between 1000 and 3000 volumes ofgas treated per volume of catalyst. I 1 A p o r Prepa a i t, r t on; of ofl-gas effluent from fluidized coking for alkylation or polymerization, said ofi-gas fraction including hydrogen, butylene, iso-butane, and butane, and also butadiene in objectionable amounts, comprising reducing the butadiene content by passing said fraction substantially dry over a bed of cobalt molybdate hydrogenation catalyst at elevated temperatures in the range of 400 F. to 450- F., so that there is no substantial loss of butylene by hydrogenation thereof, while substantially all butadiene is converted to butylene.

4. A process for obtaining'increased material suitable for gasoline blendingfrom residualoil that hasbeen subjected to cracking, comprising the steps of submitting the residual oil to a fluidized coking operation, passing the hot,normally gaseous, dry fraction of the elfiuent from said operation over a cobalt molybdate catalyst bed at between 300 F. and600 F. and at a vapor space velocity between 200 and 10,000 volumes of gas per volume of catalyst so that the hydrogen contained therein reacts selectively with the butadiene therein to form butylene, fractionating the hydrogenated'efliuent, and passing the C; fraction thereof to an alkylation plant for direct reaction therein.

5. A process for obtaining increased material suitable for gasoline blending from heavy residual oil that has been subjected to cracking, comprising the steps of passing said residual oil over a fluidized bed of hot coke, fractionating the hot, normally gaseous, efliuent therefrom to obtain hydrogen and a dry 0., fraction, mixing said dry C fraction with hydrogen in the ratio of at least one mole of hydrogen per mole ofbutadiene in said C fraction, passing said mixture over a bedofcobalt molybdate at a temperature of between 300 F. and 600 F. and at a vapor space velocity between 200 and 10,000 volumesof gas per volume of catalyst to convert said butadiene to butylene and then alkylating the resultant C fraction. 

1. A PROCESS FOR ELIMINATING BUTADIENE FROM A DRY MIXTURE THEREOF WITH BUTYLENES, COMPRISING HYDROGENATING THE DRY MIXTURE IN THE PRESENCE OF COBALT MOLYBDATE CATALYST AT BETWEEN 30*F. AND 600*F. AND AT A VAPOR SPACE VELOCITY BETWEEN 200 AND 10,000 VOLUMES OF GAS PER VOLUME OF CATALYST, TO CONVERT THE BUTADIENE TO BUTYLENE WHILE LEAVING THE ORIGINAL BUTYLENE SUBSTANTIALLY UNCHANGED. 